Black ink composition excellent in black

ABSTRACT

An ink composition excellent in blackness and storage stability is disclosed which comprises a first dye represented by the following general formula (I) and a second dye selected from the group consisting of C.I. Direct Yellow 86, 132 and 144 and compounds represented by the following general formulae (II) and (III): ##STR1##

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an ink composition excellent inblackness and an ink jet recording method using the same.

2. Background Art

A black ink is an important ink composition used as an ink jet recordingink composition for both monocolor and full color printings.

C.I. Food Black 2 (Japanese Patent Laid-Open No. 93766/1984) and dyeshaving structures analogous thereto (Japanese Patent Laid-Open No.91577/1991) have been widely used as dyes for the black ink.

These dyes, however, have a somewhat bluish hue that is more or lessdifferent from pure black (a black color perceived, for example, fromChinese ink (sumi) or Japanese lacquer (urushi)).

For this reason, a proposal has been made on the use of a combination ofthese dyes with other dyes for the purpose of improving the hue(Japanese Patent Laid-Open No. 36279/1990). However, it has been foundthat the combination of dyes deteriorates the storage stability of theink. Furthermore, the use of such an ink in ink jet printers, whicheffect printing at a high density of 300 dpi or more and a highfrequency of 5 kHz or more, often gives rise to lack of jettingstability and clogging of nozzles. A special recording material (forexample, coat paper comprising a substrate sheet, such as paper, an inkreceiving layer containing a pigment and binder) has been proposed forthe purpose of enhancing the image quality. Although the coat paper canprovide pure black, it is desired that blackness and sharpness of animage will be also performed on plain paper.

In a water-base ink using a water-soluble dye, a general problem is toimprove the water resistance of the print (for example, Japanese PatentLaid-Open Nos. 91577/1991, 226175/1992 and 233975/1992). The inkcomposition described in these Japanese Patent Laid-Open No. 36279/1990also leaves room for an improvement in the water resistance of theprint.

Additional properties which are generally required of ink compositionsfor an ink jet recording method are that the ink does not clog jettingnozzles, printing can be quickly resumed even though clogging occurred,and ink properties remain unchanged during storage. Therefore, the inkcompositions for ink jet recording should satisfy requirements offreedom from clogging of nozzles, quick resumption of printing afterclogging of nozzles and excellent storage stability in addition to pureblack color and water resistance.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide an inkcomposition excellent in blackness and storage stability and an ink jetrecording method using the same.

Another object of the present invention is to provide an ink compositionexcellent in blackness even on plain paper and forming a sharp image andan ink jet recording method using the same.

A further object of the present invention is to provide an inkcomposition capable of satisfying requirements of not only waterresistance but also various properties required of ink compositions forink jet recording, for example, no clogging of nozzles and excellentstorage stability.

The present inventors have found that a combination of two dyes having aparticular structure can provide an ink composition excellent inblackness, resumption of printing after clogging and storage stability.

The ink composition according to the present invention comprises a firstdye represented by the general formula (I): ##STR2## wherein R¹represents a phenyl or naphthyl group which may be substituted by ahydroxyl group, --NH₂, --SO₃ M or --COOM wherein M represents a hydrogenatom or a cation species derived from an alkali metal, ammonia or anamine,

R² represents a carboxyalkyl group wherein the carboxy group may form asalt with an alkali metal or ammonia, a substituted or unsubstitutedalkoxyalkyl group or a substituted or unsubstituted phenyl or alkanoylgroup, and

R³, R⁴ and R⁵, which may be the same or different, each independentlyrepresent a hydrogen atom or --SO₃ M wherein M is as defined above,

provided that R¹ does not represent a phenyl group substituted with--SO₃ M when R³, R⁴ and R⁵ all represent --SO₃ M;

and a second dye selected from the group consisting of C.I. DirectYellow 86, 132 and 144 and compounds represented by formula (II):##STR3## wherein R⁶ represents a phenyl or naphthyl group which may besubstituted by a hydroxyl group, --NH₂, --SO₃ M or --COOM wherein Mrepresents a hydrogen atom or a cation species derived from an alkalimetal, ammonia or an amine, and

R⁷ represents a hydrogen atom or --SO₃ M wherein M is as defined above;or formula (III): ##STR4## wherein R⁸ and R⁹, which may be the same ordifferent, each independently represent a hydrogen atom, an alkyl groupor a hydroxyalkyl group, provided that R⁸ and R⁹ do not simultaneouslyrepresent a hydrogen atom, and

R¹⁰ and R¹¹, which may be the same or different, each independentlyrepresent a hydrogen atom, an alkyl group, a hydroxyalkyl group or analkoxy group.

DETAILED DESCRIPTION OF THE INVENTION

First Dye

The first dye used in the ink composition according to the presentinvention is a compound represented by the general formula (I). Thecompound represented by the general formula (I) is a dye that, as such,may be used as a dye for a black ink. In the present invention, it isadded in combination with dyes, which will be described below, toprovide an ink composition.

In the general formula (I), the phenyl group or naphthyl group as the R¹may be unsubstituted or substituted. When the R¹ represents asubstituted phenyl group, a monosubstituted (preferably 3- or4-substituted) phenyl group or a disubstituted (preferably2,4-disubstituted or 3,5-disubstituted) phenyl group. Preferred examplesof the substituent include a hydroxyl group, --NH₂, a sulfonic group anda carboxy group. The sulfonic group and carboxy group may be in the formof a free acid or a salt. Preferred examples of the salt include saltsof sulfonic acid and carboxylic acid with an alkali metal, ammonia oramine (preferably tri(hydroxy C₁₋₆ alkyl)amine).

The naphthyl group as the R¹ may be 1- or 2-naphthyl and unsubstitutedor substituted. When the R¹ represents a substituted naphthyl, preferredexamples of the substituent include those described above in connectionwith the phenyl group.

In the general formula (I), the carboxyalkyl group as the R² ispreferably a carboxyC₁₋₆ alkyl group, still preferably a carboxy C₁₋₄alkyl group. The carboxy group preferably combines with an alkali metalor ammonia to form a salt. The alkoxyalkyl group as the R² is preferablya C₁₋₆ alkoxyC₁₋₆ alkyl group, still preferably C₁₋₄ alkoxyC₁₋₄ alkylgroup. One or more hydrogen atoms present in the alkoxyalkyl group maybe substituted, and preferred examples of the substituent include ahydroxyl group and --NH₂. The phenyl group as the R² may be substituted,and preferred examples of the substituent include a hydroxyl group and--NH₂. The alkanoyl group as the R² is preferably a C₁₋₆ alkanoyl group,still preferably C₁₋₄ alkanoyl group.

In the general formula (I), the R³, R⁴ and R⁵ may be the same ordifferent and each independently represent a hydrogen atom or a sulfonicgroup. The sulfonic group may be in the form of a free acid or a salt.Preferred examples of the salt include salts of sulfonic acid with analkali metal, ammonia or amine (preferably tri(hydroxy C₁₋₆alkyl)amine).

It is noted that compounds represented by the general formula (I)wherein R¹ represents a phenyl group substituted with --SO₃ M and R³, R⁴and R⁵ all represent --SO₃ M cannot be utilized in the ink compositionof the present invention. This is because experiments conducted by thepresent inventors have revealed that these compounds do not exhibitfavorable properties.

Specific preferred examples of the compound represented by the generalformula (I) are as follows.

    __________________________________________________________________________     ##STR5##                                                                     Compound                                                                      No.   R.sup.1      R.sup.2    R.sup.3 *  R.sup.4    R.sup.5                   __________________________________________________________________________     1                                                                                   ##STR6##    H          H          SO.sub.3 Na                                                                              SO.sub.3 Na                2                                                                                   ##STR7##    CH.sub.2 COOLi                                                                           SO.sub.3 Li                                                                              SO.sub.3 Li                                                                              H                          3                                                                                   ##STR8##    COCH.sub.3 SO.sub.3 Na                                                                              SO.sub.3 Na                                                                              SO.sub.3 Na                4                                                                                   ##STR9##                                                                                   ##STR10## SO.sub.3 NH.sub.4                                                                        SO.sub.3 NH.sub.4                                                                        H                          5                                                                                   ##STR11##   H          SO.sub.3 NH.sub.4                                                                        SO.sub.3 NH.sub.4                                                                        H                          6                                                                                   ##STR12##                                                                                  ##STR13## H          SO.sub.3 Na                                                                              H                          7                                                                                   ##STR14##   H          H          H          SO.sub.3 NH.sub.4          8                                                                                   ##STR15##   H          SO.sub.3 Na                                                                              SO.sub.3 Na                                                                              H                          9                                                                                   ##STR16##   H          SO.sub.3 NH.sub.4                                                                        SO.sub.3 NH.sub.4                                                                        H                         10                                                                                   ##STR17##   CH.sub.2 COONa                                                                           SO.sub.3 Na                                                                              SO.sub.3 Na                                                                              H                         11                                                                                   ##STR18##   CH.sub.2 CH.sub.2 COONH.sub.4                                                            H          SO.sub.3 NH.sub.4                                                                        H                         12                                                                                   ##STR19##   H          SO.sub.3 Li                                                                              SO.sub.3 Li                                                                              H                         13                                                                                   ##STR20##   H          SO.sub.3 Na                                                                              SO.sub.3 Na                                                                              SO.sub.3 Na               14                                                                                   ##STR21##                                                                                  ##STR22## H          SO.sub.3 Na                                                                              H                         15                                                                                   ##STR23##   CH.sub.2 COONa                                                                           H          SO.sub.3 Na                                                                              SO.sub.3 Na               16                                                                                   ##STR24##   CH.sub.2 CH.sub.2 COOLi                                                                  SO.sub.3 Li                                                                              SO.sub.3 Li                                                                              H                         17                                                                                   ##STR25##   H          SO.sub.3 Li                                                                              SO.sub.3 Li                                                                              H                         18                                                                                   ##STR26##   COCH.sub.3 H          SO.sub.3 NH.sub.4                                                                        SO.sub.3 NH.sub.4         19                                                                                   ##STR27##   H          SO.sub.3 Na                                                                              H          SO.sub.3 Na               20                                                                                   ##STR28##   H          SO.sub.3 NH.sub.4                                                                        SO.sub.3 NH.sub.4                                                                        H                         21                                                                                   ##STR29##   H          H          SO.sub.3 Na                                                                              SO.sub.3 Na               22                                                                                   ##STR30##   H          SO.sub.3 NH.sub.4                                                                        SO.sub.3 NH.sub.4                                                                        H                         23                                                                                   ##STR31##   COCH.sub.3 SO.sub.3 NH(C.sub.2 H.sub.5 OH).sub.3                                                    SO.sub.3 NH(C.sub.2 H.sub.5                                                              HH)                       __________________________________________________________________________

The dyes represented by the general formula (I) can be produced by knownmethods and methods similar thereto. For example, the dyes representedby the general formula (I) can be produced by a method described inJapanese Patent Laid-Open No. 140270/1990 and Colour Index, ThirdEdition, the Society of Dyers and Colourists.

Second Dye

The second dye used in the ink composition of the present invention is adye selected from the group consisting of C.I. Direct Yellow 86, 132 and144 and compounds represented by the following general formulae (II) and(III).

C.I. Direct Yellow 86, 132 and 144 are described in, for example, ColorIndex, Third Edition.

The compounds represented by the general formula (II) are those that, assuch, may be used as a dye. In the general formula (II), the phenylgroup or naphthyl group as the R⁶ may be unsubstituted or substituted.When the R⁶ represents a substituted phenyl group, preferred examples ofthe substituent include a hydroxyl group, --NH₂, a sulfonic group and acarboxy group. The sulfonic group and carboxy group may be in the formof a free acid or a salt. Preferred examples of the salt include saltsof sulfonic acid and carboxylic acid with an alkali metal, ammonia oramine (preferably tri(hydroxy C₁₋₆ alkyl)amine). Although there is noparticular limitation on the position of the substituent, thesubstituent is preferably located at the 3- or 4-position. The naphthylgroup as the R⁶ may be either 1-naphthyl or 2-naphthyl and unsubstitutedor substituted. When the R¹ represents a substituted naphthyl group,preferred examples of the substituent include those described above inconnection with the phenyl group.

Specific preferred examples of the compound represented by the generalformula (II) are as follows.

    ______________________________________                                         ##STR32##                                                                    Com-                                                                          pound                                                                         No.   R.sup.6             R.sup.7 *                                           ______________________________________                                         1                                                                                   ##STR33##          SO.sub.3 Na                                          2                                                                                   ##STR34##          H                                                    3                                                                                   ##STR35##          H                                                    4                                                                                   ##STR36##          H                                                    5                                                                                   ##STR37##          SO.sub.3 Na                                          6                                                                                   ##STR38##          SO.sub.3 NH.sub.4                                    7                                                                                   ##STR39##          SO.sub.3 Na                                          8                                                                                   ##STR40##          SO.sub.3 N(C.sub.2 H.sub.5 OH).sub.3 H               9                                                                                   ##STR41##          SO.sub.3 Na                                         10                                                                                   ##STR42##          SO.sub.3 Li                                         11                                                                                   ##STR43##          SO.sub.3 Na                                         12                                                                                   ##STR44##          H                                                   13                                                                                   ##STR45##          H                                                   14                                                                                   ##STR46##          H                                                   15                                                                                   ##STR47##          SO.sub.3 Li                                         16                                                                                   ##STR48##          SO.sub.3 N(C.sub.2 H.sub.5 OH).sub.3 H              17                                                                                   ##STR49##          SO.sub.3 Na                                         18                                                                                   ##STR50##          H                                                   19                                                                                   ##STR51##          H                                                   20                                                                                   ##STR52##          H                                                   ______________________________________                                    

The dyes represented by the general formula (II) can be produced byknown methods and methods similar thereto. For example, the dyesrepresented by the general formula (II) are described as an intermediateof black dyes in Japanese Patent Laid-Open No. 140270/1990 and can beproduced according to a method described therein.

As with the compounds represented by the general formula (II), thecompounds represented by the general formula (III) are those that, assuch, may be used as a dye. In the general formula (III), the alkylgroup as the R⁸ and R⁹ is preferably a C₁₋₆ alkyl group, stillpreferably a C₁₋₄ alkyl group. The hydroxyalkyl group as the R⁸ and R⁹is preferably a hydroxy C₁₋₆ alkyl group, still preferably a hydroxyC₁₋₄ alkyl group. Compounds represented by the general formula (III)wherein R⁸ and R⁹ simultaneously represent a hydrogen atom are excludedfrom the scope of the present invention. In the general formula (III),the alkyl group as the R¹⁰ and R¹¹ is preferably a C₁₋₆ alkyl group,still preferably a C₁₋₄ alkyl group. The alkoxy group as the R¹⁰ and R¹¹is preferably a C₁₋₆ alkoxy group, still preferably a C₁₋₄ alkoxy group.

Specific preferred examples of the compound represented by the generalformula (III) are as follows.

    __________________________________________________________________________     ##STR53##                               (III)                                Compound                                                                      No.    M        R.sup.8                                                                              R.sup.9                                                                              R.sup.10                                                                             R.sup.11                                 __________________________________________________________________________    1      Na       H      C.sub.2 H.sub.5 OH                                                                   H      H                                        2      NH.sub.4 H      C.sub.2 H.sub.5 OH                                                                   CH.sub.3                                                                             CH.sub.3                                 3      NH.sub.4 H      C.sub.2 H.sub.5 OH                                                                   OCH.sub.3                                                                            OCH.sub.3                                4      Li       C.sub.2 H.sub.5 OH                                                                   C.sub.2 H.sub.5 OH                                                                   CH.sub.3                                                                             CH.sub. 3                                5      NH.sub.4 C.sub.2 H.sub.5 OH                                                                   C.sub.2 H.sub.5 OH                                                                   CH.sub.3                                                                             CH.sub.3                                 6      Na       CH.sub.3                                                                             C.sub.2 H.sub.5 OH                                                                   OCH.sub.3                                                                            OCH.sub.3                                7      Na       CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                            OCH.sub.3                                8      NH.sub.4 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      CH.sub.3                                                                             CH.sub.3                                 9      NH(C.sub.2 H.sub.5 OH).sub.3                                                           H      C.sub.2 H.sub.5 OH                                                                   OCH.sub.3                                                                            OCH.sub.3                                __________________________________________________________________________

The dyes represented by the general formula (III) can be produced byknown methods and methods similar thereto. For example, the dyesrepresented by the general formula (III) can be produced by a methoddescribed in Japanese Patent Laid-Open No. 179100/1991 and Colour Index,Third Edition.

Ink Composition

In the ink composition according to the present invention, the contentof the dye represented by the general formula (I) is preferably 0.1 to10% by weight, still preferably 1 to 5% by weight. When the content ofthe dye represented by the general formula (I) is less than the aboverange, no satisfactory print density is often provided. On the otherhand, when it exceeds the above range, since the dissolution stabilityof the dye is deteriorated, clogging of nozzles often occurs. The dyesrepresented by the general formula (I) may be added alone or in the formof a mixture of two or more of them.

According to the present invention, an ink composition excellent inblackness can be provided by incorporating the first dye in combinationwith the second dye.

In the ink composition according to the present invention, the contentof C.I. Direct Yellow 86, 132 or 144 as the second dye is preferably inthe range of from 0.001 to 0.5% by weight, still preferably in the rangeof from 0.005 to 0.4% by weight.

When the second dye is a dye represented by the general formula (II),the content of the dye represented by the general formula (II) ispreferably in the range of from 0.001 to 0.5% by weight, stillpreferably in the range of from 0.05 to 0.4% by weight.

When the second dye is a dye represented by the general formula (III),the content of the dye represented by the general formula (III) in theink composition according to the present invention is preferably in therange of from 0.005 to 0.5% by weight, still preferably in the range offrom 0.01 to 0.04% by weight.

These second dyes may be added alone or in the form of a mixture of twoor more of them.

The solvent for the ink composition of the present invention may bewater or a mixed solvent comprising water and a water-soluble organicsolvent, and the mixed solvent comprising water and a water-solubleorganic solvent is preferred. Examples of the water-soluble organicsolvent used in the form of a mixture with water include lower alcohols,such as ethanol, 1-propanol and 2-propanol; polyhydric alcohols, such asethylene glycol, diethylene glycol, triethylene glycol, propylene glycoland glycerin; ethers of polyhydric alcohols, such as ethylene glycolmonomethyl ether, diethylene glycol monobutyl ether and propylene glycolmonoethyl ether; nitrogen-containing compounds, such as formamide,dimethylformamide, diethanolamine, triethanolamine,1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone and N-methyl-2pyrrolidone;and sulfur-containing compounds, such as thiodiglycol anddimethylsulfoxide.

In particular, the addition of nitrogen-containing compounds, such as1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone andN-methyl-2-pyrrolidone, is preferred from the viewpoint of quickresumption of normal printing after clogging, and the amount of additionthereof is preferably in the range of from about 1 to 10% by weight.

The addition of triethanolamine is preferably in the range of from about0.5 to 2% by weight from the viewpoint of color development of the dyeand printing density.

Further dyes may be added to the ink composition of the presentinvention so far as the addition thereof is not detrimental to blacknessof the ink and other effects. According to a preferred embodiment of thepresent invention, the addition of dyes having a surface activity isadvantageous. The addition of such dyes having a surface activity cancontribute to an improvement in the wettability of the recording headand ink path by the ink composition. As a result, bubbles, which haveintruded into the recording head and ink path, can be easily discharged.Specific examples of the dyes of this type include C.I. Direct Black 154and 168.

Furthermore, if necessary, various additives may be added to the inkcomposition of the present invention for the purpose of improvingvarious properties of the ink composition. For example, resins,polymers, surfactants, pH adjustors, fungicides and ultravioletabsorbers may be added.

EXAMPLES

The present invention will now be described in more detail withreference to the following Examples, though it is not limited to theseExamples only.

Production of Ink Composition

Ink compositions comprising components specified in the following Tables1 to 5, that is, ink compositions of Examples A1 to A10, B1 to B10, C1to C12, D1 to D10 and E1 to Ell and Comparative Examples A1 to A3, B1 toB3, C1 to C3, D1 to D3 and E1 to E3 were produced as follows.Specifically, individual components were mixed with each other, and themixtures were filtered under pressure through a membrane filter having apore diameter of 0.8 μm. Thereafter, the filtrates were deaerated with avacuum pump to provide ink compositions.

In the tables, the balance of the components consists of water.

Evaluation Test

Various properties of the ink compositions of Examples and ComparativeExamples were evaluated by the following methods. The results were asgiven in the tables.

In the evaluation test, print samples and 100% duty print samples wereprovided by printing with an ink jet printer HG-5130 (manufactured bySeiko Epson Corporation) using the ink compositions of Examples andComparative Examples. In the tables, the results of evaluation given inparentheses were obtained by an evaluation test effected in the samemanner as that described just above, except that use was made of an inkjet printer BJ-330 (manufactured by Canon Inc.). Further, in theevaluation tests (2) to (6), recording paper (a) is an ink jet coatpaper NM available from Mitsubishi Paper Mills, Ltd., recording paper(b) Cannon Dry available from Canon Sales Co., Inc., recording paper (c)Xerox 4024 available from Xerox Co., (d) Xerox P available from FujiXerox Co., Ltd. and recording paper (e) Recopy 6200 available from RicohCo., Ltd.

Evaluation test 1: Water resistance

(1) Water droplets were dropped onto a printed portion of the printsample which was then spontaneously dried and observed to evaluate thewater resistance under the following criteria.

⊚: No change from the initial state observed.

◯: Slight dissolution of dye observed with letters being still legible.

Δ: Blurring observed with letters being still legible.

×: Blurring of letters observed with letters being illegible.

(2) The 100% duty print sample was immersed in water for 24 hr. Then, aOD retention was determined by the following equation: ##EQU1##

Evaluation test 2: Blackness

Tone of the 100% duty print samples on recording paper (a) to (e) wasobserved with the naked eye. The criteria of the evaluation were asfollows.

⊚: Substantially pure black with good vividness

◯: Pure black with slight lack of vividness

Δ: Pure black with poor vividness

×: Color close to black but different from black in hue

Evaluation test 3: Resumption of normal printing after clogging

An ink jet printer HG-5130 was filled with the ink composition andallowed to stand at 40° C. for one month without capping the recordinghead. Thereafter, the number of times of cleaning operation necessaryfor resuming normal printing was determined. The criteria of theevaluation were as follows.

⊚: 0 to twice

◯: 3 to 5 times

Δ: 5 times or more

×: Not resumable

Evaluation test 4: Jetting stability

(1) Printing was continuously effected on 1000 sheets of recording paperusing a piezo drive on-demand ink jet recording head (48 nozzles,diameter 40 μm) at a driving frequency of 7.2 kHz and 10 kHz. Theresults were evaluated as follows.

◯: Successful printing without abnormal phenomenon

×: Failure of jetting and turbulence of print

(2) Bubbles were intentionally introduced into the head of the ink jetprinter, and the number of times of cleaning operation necessary forresuming normal printing was determined. The criteria of the evaluationwere as follows.

⊚: once

◯: 2 to 3 times

Δ: 4 to 5 times

×: 5 times or more or not resumable

Evaluation test 5: Storage stability

The ink composition was hermetically sealed in a glass vessel andallowed to stand at -30° C. and 70° C. for one month, and observationwas effected on a change in the properties of the ink, a change in thetone and precipitation of insolubles after standing. The results wereevaluated as follows.

◯: Neither a change in the properties and tone nor occurrence of aprecipitate observed.

Δ: A change in the properties or tone observed.

×: A change in the properties or tone or occurrence of a precipitateobserved.

Evaluation test 6: Quality of image

The print was observed with the naked eye to evaluate the sharpness ofthe image in terms of blurring and density according to the followingcriteria.

⊚: No blurring and a high density

◯: Slight blurring without determent to image and a high density

×: Severe blurring and a low density

Evaluation test 7: Light fastness

The 100% duty print samples were irradiated with light for 50 hr using axenon fadeometer, and the change in the OD value between beforeirradiation and after irradiation was determined. The results wereevaluated as follows.

◯: 0 to less than 5%

Δ: 5 to less than 10%

×: 10% or more

                                      TABLE 1                                     __________________________________________________________________________               Examples                                Comparative Examples                  A1  A2  A3  A4  A5  A6  A7  A8  A9  A10 A1  A2  A3                 __________________________________________________________________________    First dye  4   7   8   12  13  14  17  2   7   10(0.5)                                                                           4   12  7                  General formula (I)                                                                      (2) (2.5)                                                                             (4) (3) (2) (2.5)                                                                             (5) (3) (9) 15(0.5)                                                                           (2) (3) (10)               Compd. No. (wt. %)                                                            Second dye 6   4   7   10  7   14  15  2   4(1)                               General formula (II)                                                                     (0.4)                                                                             (0.3)                                                                             (1) (0.4)                                                                             (0.1)                                                                             (0.5)                                                                             (0.5)                                                                             (1) 6(1)                                                                              (0.1)                          Compd. No. (wt. %)                                                            Ratio of dyes added                                                                      1:0.2                                                                             1:0.12                                                                            1:0.25                                                                            1:0.13                                                                            1:0.05                                                                            1:0.2                                                                             1:0.1                                                                             1:0.33                                                                            1:0.22                                                                            1:0.10                         (first):(second)                                                              Glycerin   8       6   5   3               15  5   8   5   15                 Diethylene glycol                                                                            15              10  10                                         Polyethylene glycol                10                                         #200                                                                          1,3-Propanediol                        10                                     Thiodiglycol       10                                                         1,3-Dimethyl-2-        2                               2                      imidazolidinone                                                               2-Pyrrolidone              3               10              10                 N-Methyl-2-pyrroli-                    1                                      done                                                                          Triethanolamine                1                                              Ethanol    6               5           2           6                          1-Propanol         4   3                       7       3                      2-Propanol     3.5             2                                              Leafinol 465                       1       1               1                  α-Cyclodextrin                           3                              Test 1   (1)                                                                             ⊚                                                                  ⊚                                                                  ◯                                                                     ⊚                                                                  ◯                                                                     ⊚                                                                  ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ⊚                                                                  ⊚                                                                  .circleincircle                                                               .                  Water resistance                                                                       (2)                                                                             95  90  87  92  90  90  85  88  90  82  95  90  90                 Test 2   (a)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ⊚(.circleinc                                                   ircle.)                                                                           ◯(.largecir                                                       cle.)                                                                             ◯(.larg                                                           ecircle.)                                                                         .circleincircle                                                               .(.circleincirc                                                               le.)               Blackness                                                                              (b)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  Δ(Δ)                                                                  Δ(Δ                                                               )                           (c)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   Δ(Δ)                                                                  ×(×)                                                                  Δ(Δ                                                               )                           (d)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   Δ(Δ)                                                                  ×(×)                                                                  Δ(Δ                                                               )                           (e)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   Δ(Δ)                                                                  ×(×)                                                                  Δ(Δ                                                               )                  Test 3     ⊚(⊚)                                                ◯(◯)                                                      ⊚(⊚)                                                ◯(◯)                                                      ⊚(⊚)                                                ⊚ (⊚)                                               ◯(◯)                                                      ⊚(◯)                                                   ◯(Δ)                                                            ⊚(.circleinc                                                   ircle.)                                                                           ⊚(.circl                                                       eincircle.)                                                                       ◯(.larg                                                           ecircle.)                                                                         Δ(Δ                                                               )                  Resumption after                                                              clogging                                                                      Test 4   (1)                                                                             ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯                                                   )   ◯(.largecir                                                       cle.)                                                                             ◯(.larg                                                           ecircle.)                                                                         ◯(.                                                               largecircle.)      Jetting stability                                                                      (2)                                                                             ◯                                                                     ◯                                                                     ⊚                                                                  ⊚                                                                  ⊚                                                                  ◯                                                                     ⊚                                                                  ⊚                                                                  ◯                                                                     ◯                                                                     ◯                                                                     ⊚                                                                  ◯      Test 5     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯      Storage stability                                                             Test 6   (a)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ⊚(.circleinc                                                   ircle.)                                                                           ◯(.largecir                                                       cle.)                                                                             ◯(.larg                                                           ecircle.)                                                                         .circleincircle                                                               .(.circleincirc                                                               le.)               Quality of image                                                                       (b)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ⊚(⊚)                                                ◯(◯)                                                      ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)               (c)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)               (d)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)               (e)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)      Test 7     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     Δ                                                                           ◯                                                                     ◯      Light fastness                                                                __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________               Examples                                Comparative Examples                  B1  B2  B3  B4  B5  B6  B7  B8  B9  B10 B1  B2  B3                 __________________________________________________________________________    First dye  1   8   10  13  22  16  15  3   1(9)                                                                              11(0.5)                                                                           1   13  22                 General formula (I)                                                                      (2) (3) (5) (3) (2) (2.5)                                                                             (5) (3) 21(1)                                                                             20(0.5)                                                                           (2) (3) (10)               Compd. No. (wt. %)                                                            Second dye 0.5 1   2   0.4 0.3 0.1 0.02                                                                              0.015                                                                             4   0.05                           C.I. Direct Yellow 86                                                         (wt. %)                                                                       Ratio of dyes added                                                                      1:0.25                                                                            1:0.33                                                                            1:0.40                                                                            1:0.13                                                                            1:0.15                                                                            1:0.04                                                                            1:0.004                                                                           1:0.005                                                                           1:0.40                                                                            1:0.10                         (first):(second)                                                              Glycerin   8       6   5   3               15  5   8   5   15                 Diethylene glycol                                                                            15              10  10                                         Polyethylene glycol                10                                         #200                                                                          1,3-Propanediol                        10                                     Thiodiglycol       6                                                          1,3-Dimethyl-2-        2                               2                      imidazolidinone                                                               2-Pyrrolidone              3               10              10                 N-Methyl-2-pyrroli-                    1                                      done                                                                          Triethanolamine            1   1                                              Ethanol    6               5           2           6                          1-Propanol         4   3                       7       3                      2-Propanol     3.5             2                                              Leafinol 465                       1       1               1                  α-Cyclodextrin                           3                              Test 1   (1)                                                                             ⊚                                                                  ⊚                                                                  ◯                                                                     ⊚                                                                  ◯                                                                     ⊚                                                                  ⊚                                                                  ◯                                                                     ◯                                                                     ◯                                                                     ⊚                                                                  ⊚                                                                  ◯      Water resistance                                                                       (2)                                                                             90  95  85  87  85  90  87  90  90  92  90  87  85                 Test 2   (a)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ⊚(.circleinc                                                   ircle.)                                                                           ◯(.largecir                                                       cle.)                                                                             ◯(.larg                                                           ecircle.)                                                                         .circleincircle                                                               .                                                                             (.circleincircl                                                               e.)                Blackness                                                                              (b)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  Δ(Δ)                                                                  Δ(Δ                                                               )                           (c)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   Δ(Δ)                                                                  ×(×)                                                                  Δ(Δ                                                               )                           (d)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   Δ(Δ)                                                                  ×(×)                                                                  Δ(Δ                                                               )                           (e)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   Δ(Δ)                                                                  ×(×)                                                                  Δ(Δ                                                               )                  Test 3     ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(◯)                                                   ⊚(◯)                                                   ⊚(⊚)                                                ◯(Δ)                                                            ◯(◯)                                                      ◯(Δ                                                             ◯(◯                                                   )   ⊚(.circl                                                       eincircle.)                                                                       ⊚(.l                                                           argecircle.)                                                                      Δ(Δ                                                               )                  Resumption after                                                              clogging                                                                      Test 4   (1)                                                                             ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯                                                   )   ◯(.largecir                                                       cle.)                                                                             ◯(.larg                                                           ecircle.)                                                                         ◯(.                                                               largecircle.)      Jetting stability                                                                      (2)                                                                             ◯                                                                     ◯                                                                     ⊚                                                                  ⊚                                                                  ◯                                                                     ◯                                                                     ⊚                                                                  ⊚                                                                  ◯                                                                     ◯                                                                     ◯                                                                     ⊚                                                                  ◯      Test 5     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯      Storage stability                                                             Test 6   (a)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ⊚(.circleinc                                                   ircle.)                                                                           ◯(.largecir                                                       cle.)                                                                             ◯(.larg                                                           ecircle.)                                                                         .circleincircle                                                               .(.circleincirc                                                               le.)               Quality of image                                                                       (b)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(Δ)                                                            ⊚(⊚)                                                ◯(◯)                                                      ◯                                                                 (◯)                                                                   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)               (c)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)               (d)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)               (e)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)      Test 7     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     Δ                                                                           ◯                                                                     ◯      Light fastness                                                                __________________________________________________________________________

    TABLE 3       Examples Comparative Examples C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12     C13 C1 C2 C3       First dye 1 8 10 13 22 16 15 3 1(9) 11(0.5) 5(3) 5(3) 22(2.5) 1 13 22     General formula (I) (2) (3) (5) (3) (2) (2.5) (5) (3) 21(1) 20(0.5)     (2) (3) (10) Compd. No. (wt. %) Second dye 0.5 1 2 0.4 0.3 0.1 0.02     0.015 4 0.05 0.3 0.3 0.3 C.I. Direct Yellow           DB168*1 DB168     DB154*2 132 (wt. %)           (0.2) (0.2) (0.3) Ratio of dyes added     1:0.25 1:0.33 1:0.40 1:0.13 1:0.15 1:0.04 1:0.004 1:0.005 1:0.40 1:0.10     1:0.1 1:0.1 1:0.28 (first):(second) Glycerin 8  6 5 3    15 5 4 3 3 8 5     15 Diethylene glycol  15    10 10 Polyethylene glycol #200       10     1,3-Propanediol        10 Thiodiglycol   6 1,3-Dimethyl-2-imidazolidinone         2           2 2-Pyrrolidone     3    10  3 2 4   10 N-Methyl-2-pyrrol     idone        1 Triethanolamine     1 1     1 1 1 Ethanol 6    5   2   5     4 4 6 1-Propanol   4 3      7     3 2-Propanol  3.5    2 Leafinol 465        1  1       1 α     Cyclodextrin          3 Test 1 (1) ⊚ ⊚     ◯ ⊚ ◯ ⊚ .circleinci     rcle. ◯ ◯ ◯ ⊚     ⊚ ◯ ⊚ ⊚     ◯ Water resistance (2) 90 95 86 88 85 90 90 90 90 92 95 95     88 90 88 83 Test 2 (a) ⊚(⊚) .circleincircle     .(⊚) ⊚(⊚) ⊚(.     circleincircle.) ⊚(⊚) ⊚(.cir     cleincircle.) ⊚(⊚) ⊚(.circle     incircle.) ⊚(⊚) ⊚(.circleinc     ircle.) ⊚(⊚) ⊚ .circleincirc     le.(⊚) ◯(◯) ◯(.largeci     rcle.) ⊚(⊚) Blackness (b) ⊚(     ⊚) ⊚(⊚) ⊚(.ci     rcleincircle.) ⊚(⊚) ⊚(.circl     eincircle.) ⊚(⊚) ◯(.largecircle     .) ◯(◯) ⊚(⊚)     ◯(◯) ⊚(⊚) .circlein     circle. ⊚(⊚) ×(×) Δ(.DELT     A.) Δ(Δ)  (c) ⊚(⊚) .circleincir     cle.(⊚) ⊚(⊚) .circleincircle     .(⊚) ⊚(⊚) ⊚(.     circleincircle.) ◯(◯) ◯(◯     ) ⊚(⊚) ◯(◯)     ⊚(⊚) ⊚ ⊚(.cir     cleincircle.) Δ(Δ) ×(×) Δ(Δ)  (d)     ⊚(⊚) ⊚(⊚)     ⊚(⊚ ) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ◯(◯) ◯(◯) .circleincircle     .(⊚) ◯(◯) ⊚(.circle     incircle.) ⊚ ⊚(⊚) Δ(.D     ELTA.) ×(×) Δ(Δ)  (e) ⊚(.circleinc     ircle.) ⊚(⊚) ⊚(.circleincirc     le.) ⊚(⊚) ⊚(⊚     ) ⊚(⊚) ◯(◯)     ◯(◯) ⊚(⊚) .largecir     cle.(◯) ⊚(⊚) ⊚     ⊚(⊚) Δ(Δ) ×(×)     Δ(Δ) Test 3  ⊚(⊚) .circleincirc     le.(⊚) ⊚(⊚) ⊚     (◯) ⊚(◯) ⊚(.circlei     ncircle.) ◯(Δ) ◯(◯) .largecircl     e.(Δ) ◯(◯) ⊚(.circleincircle     .) ⊚ ⊚(◯) ⊚(.cir     cleincircle.) ⊚(◯) Δ(Δ) Resumption      after clogging Test 4 (1) ◯(◯) ◯(.la     rgecircle.) ◯(◯) ◯(◯)     ◯(◯) ◯(◯) ◯(.     largecircle.) ◯(◯) ◯(◯)     ◯(◯) ◯(◯) .circleincircle     . ⊚(◯) ◯(◯) .largecirc     le.(◯) ◯(◯) Jetting stability (2)     ◯  ⊚ ⊚ ⊚     ◯ ◯ ⊚ ⊚ .largecircl     e. ◯ ⊚ ⊚ ⊚     ◯ ⊚ ◯ Test 5  ◯     ◯ ◯ ◯ ◯ ◯     ◯ ◯ ◯ ◯ ◯     ◯ ◯ ◯ ◯ ◯     Test 6 (a) ⊚(⊚) ⊚(.circleinc     ircle.) ⊚(⊚) ⊚(.circleincirc     le.) ⊚(⊚) ⊚(⊚     ) ⊚(⊚) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ⊚(⊚) ◯ ⊚(.circle     incircle.) ◯(◯) ◯(◯)     ⊚(⊚) Quality of image (b) ⊚(     ⊚) ⊚(⊚) ⊚(.ci     rcleincircle.) ⊚(⊚) ⊚(.circl     eincircle.) ⊚(⊚) ◯(Δ)     ⊚(⊚) ◯(◯) .largecir     cle.(◯) ⊚(⊚) ◯     ⊚(⊚) ×(×) ×(×)     ◯(◯)  (c) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ◯(◯) ⊚(⊚) .largecir     cle. ⊚(⊚) ×(×) ×(×)      ◯(◯)  (d) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ◯(◯) ⊚(⊚) .largecir     cle. ⊚(⊚) ×(×) ×(×)      ◯(◯)  (e) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ⊚(⊚) ◯(◯) .circlein     circle.(⊚) ⊚(⊚) .largecircle     .(◯) ⊚(⊚) ◯     ⊚(⊚) ×(×) ×(×)     ◯(◯) Test 7  ◯ ◯     ◯ ◯ ◯ ◯ ◯     ◯ ◯ ◯ ◯ ◯     ◯ Δ ◯ ◯ Light fastness

                                      TABLE 4                                     __________________________________________________________________________               Examples                                Comparative Examples                  D1  D2  D3  D4  D5  D6  D7  D8  D9  D10 D1  D2  D3                 __________________________________________________________________________    First dye  1   8   10  13  22  16  15  3   1(9)                                                                              11(0.5)                                                                           1   13  22                 General formula (I)                                                                      (2) (3) (5) (3) (2) (2.5)                                                                             (5) (3) 21(1)                                                                             20(0.5)                                                                           (2) (3) (10)               Compd. No. (wt. %)                                                            Second dye 0.5 1   2   0.4 0.3 0.1 0.02                                                                              0.015                                                                             4   0.05                           C.I. Direct Yellow                                                            144 (wt. %)                                                                   Ratio of dyes added                                                                      1:0.25                                                                            1:0.33                                                                            1:0.40                                                                            1:0.13                                                                            1:0.15                                                                            1:0.04                                                                            1:0.004                                                                           1:0.005                                                                           1:0.40                                                                            1:0.10                         (first):(second)                                                              Glycerin   8       6   5   3               15  5   8   5   15                 Diethylene glycol                                                                            15              10  10                                         Polyethylene glycol                10                                         #200                                                                          1,3-Propanediol                        10                                     Thiodiglycol       6                                                          1,3-Dimethyl-2-        2                               2                      imidazolidinone                                                               2-Pyrrolidone              3               10              10                 N-Methyl-2-pyrroli-                    1                                      done                                                                          Triethanolamine            1   1                                              Ethanol    6               5           2           6                          1-Propanol         4   3                       7       3                      2-Propanol     3.5             2                                              Leafinol 465                       1       1               1                  α-Cyclodextrin                           3                              Test 1   (1)                                                                             ⊚                                                                  ⊚                                                                  ◯                                                                     ⊚                                                                  ◯                                                                     ⊚                                                                  ⊚                                                                  ◯                                                                     ◯                                                                     ◯                                                                     ⊚                                                                  ⊚                                                                  ◯      Water resistance                                                                       (2)                                                                             90  94  85  88  85  90  88  88  90  90  90  87  85                 Test 2   (a)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ⊚(.circleinc                                                   ircle.)                                                                           ◯(.largecir                                                       cle.)                                                                             ◯(.larg                                                           ecircle.)                                                                         .circleincircle                                                               .                                                                             (.circleincircl                                                               e.)                Blackness                                                                              (b)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  Δ(Δ)                                                                  Δ(Δ                                                               )                           (c)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   Δ(Δ)                                                                  ×(×)                                                                  Δ(Δ                                                               )                           (d)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   Δ(Δ)                                                                  ×(×)                                                                  Δ(Δ                                                               )                           (e)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ◯(◯)                                                      ⊚(.circleincircl                                               e.) ◯(◯                                                   )   Δ(Δ)                                                                  ×(×)                                                                  Δ(Δ                                                               )                  Test 3     ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(◯)                                                   ⊚(◯)                                                   ⊚(⊚)                                                ◯(Δ)                                                            ◯(◯)                                                      ◯(Δ                                                             ◯(◯                                                   )   ⊚(.circl                                                       eincircle.)                                                                       ⊚(.l                                                           argecircle.)                                                                      Δ(Δ                                                               )                  Resumption after                                                              clogging                                                                      Test 4   (1)                                                                             ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯)                                                      ◯(◯                                                   )   ◯(.largecir                                                       cle.)                                                                             ◯(.larg                                                           ecircle.)                                                                         ◯(.                                                               largecircle.)      Jetting stability                                                                      (2)                                                                             ◯                                                                     ⊚                                                                  ⊚                                                                  ⊚                                                                  ◯                                                                     ◯                                                                     ⊚                                                                  ⊚                                                                  ◯                                                                     ◯                                                                     ◯                                                                     ⊚                                                                  ◯      Test 5     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯      Storage stability                                                             Test 6   (a)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ⊚(.circleinc                                                   ircle.)                                                                           ◯(.largecir                                                       cle.)                                                                             ◯(.larg                                                           ecircle.)                                                                         .circleincircle                                                               .(.circleincirc                                                               le.)               Quality of image                                                                       (b)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(Δ)                                                            ⊚(⊚)                                                ◯(◯)                                                      ◯                                                                 (◯)                                                                   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)               (c)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)               (d)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)               (e)                                                                             ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ⊚(⊚)                                                ◯(◯)                                                      ⊚(⊚)                                                ⊚(.circleincircl                                               e.) ◯(◯                                                   )   ×(×)                                                                  ×(×)                                                                  ◯(.                                                               largecircle.)      Test 7     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     Δ                                                                           ◯                                                                     ◯      Light fastness                                                                __________________________________________________________________________

    TABLE 5       Examples Comparative Examples E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 E1 E2 E     3       First dye 1 2 5 7 13 18 23 5(4) 22(10) 5(0.5) 5(2) 1 5(4) 1 General     formula (I) (3) (3) (2) (2.5) (2) (3) (3) 7(4)  22(0.5)  (3) 7(4) (3)     Compd. No. (wt. %) Second dye 1(1) 4(1.5) 2(0.3) 3(0.1) 6(0.1) 5(0.03)     9(0.3) 3(2) 2(0.09) 8(0.05) 3(0.4)   DB154*2 General formula (III)         DB168*1   (1) Compd. No. (wt. %)           (0.2) Ratio of dyes added     1:0.33 1:0.50 1:0.15 1:0.04 1:0.05 1:0.01 1:0.1 1:0.25 1:0.009 1:0.05     1:0.3 Glycerin 6  3 4 10   15  5 3 6 15 4 Diethylene glycol  15    15     10 Polyethylene glycol #200         10 1,3-Propanediol       10 Thiodigly     col 1,3-Dimethyl-2-imidazolidinone    2 2-Pyrrolidone   3     10   3  10     N-Methyl-2-pyrrolidone       1 Triethanolamine 0.5  1 1.4 2 1     1 0.5     1.4 Ethanol 4  4  5  2    4 4 1-Propanol    3      7    3 2-Propanol     3.5    3 Leafinol 465        1 1   1 α     Cyclodextrin          3 Test I (1) ⊚ ⊚     ⊚ ⊚ ⊚ ⊚     ⊚ ⊚ ⊚ ⊚     ⊚ ⊚ ⊚ Δ Water     resistance (2) 92 90 95 90 88 88 92 87 90 94 90 90 90 Test 2 (a)     ⊚ ⊚  ⊚ ⊚     ⊚ ⊚ ⊚ ⊚     ◯ ⊚ ⊚ ◯ .largecircl     e. ◯ Blackness (b) ⊚ ◯ .circleinci     rcle. ⊚ ◯ ⊚ ◯     ⊚ ◯ ◯ ⊚ ×     × ◯  (c) ◯ ◯ ⊚     ⊚ ◯ ◯ ◯ ◯     ◯ ◯ ⊚ Δ Δ .largecircle     .  (d) ⊚ ◯ ⊚ ⊚     ◯ ⊚ ⊚ ◯ .largecircl     e. ◯ ⊚ Δ Δ ◯  (e)     ⊚ ◯ ⊚ ⊚     ◯ ⊚ ⊚ ⊚     ◯ ◯ ⊚ ◯ ◯     ◯ Test 3  ⊚(⊚) ⊚     (◯) ⊚(⊚) ⊚(.circ     leincircle.) ⊚(⊚) ◯(.largecircl     e.) ⊚(⊚) ⊚(⊚)      ◯(Δ) ⊚(⊚) .circleincircl     e.(◯) ×(×) ×(×) ×(×)     Resumption after clogging Test 4 (1) ◯(◯)     ◯(◯) ◯(◯) ◯(.     largecircle.) ◯(◯) ◯(◯)     ◯(◯) ◯(◯) ◯(.     largecircle.) ◯(◯) ◯(◯)     ×(×) ×(×) ×(×) Jetting stability (2)     ◯ ⊚ ⊚ ◯ .circleinci     rcle. ⊚ ⊚ ◯ ◯     ◯ ⊚ ◯  ⊚ Test 5     ◯ ◯ ◯ ◯ ◯     ◯ ◯ ◯ ◯ ◯     ◯ ◯ Δ × Test 6 (a) ⊚(.     circleincircle.) ⊚(⊚) ⊚(.cir     cleincircle.) ⊚(⊚) ⊚(.circle     incircle.) ⊚(⊚) ⊚(.circleinc     ircle.) ⊚(⊚) ⊚(.circleincirc     le.) ⊚(⊚) ⊚(⊚     ) ◯(◯) ◯(◯) .circleincirc     le.(⊚) Quality of image (b) ⊚(.circleincirc     le.) ◯(◯) ⊚(⊚)     ⊚(⊚) ⊚(⊚)     ◯(◯) ◯(◯) ◯(.     largecircle.) ◯(◯) ⊚(.circleincirc     le.) ⊚(⊚) ×(×) ◯(.l     argecircle.) ×(× )  (c) ⊚(⊚)     ◯(◯) ⊚(⊚) .circlein     circle.(⊚) ⊚(⊚) .largecircle     .(◯) ◯(◯) ◯(◯     ) ◯(◯) ⊚(⊚)     ⊚(⊚) ×(×) ◯(.largec     ircle.) ×(×)  (d) ⊚(⊚)     ◯(◯) ⊚(⊚) .circlein     circle.(⊚) ⊚(⊚) .largecircle     .(◯) ◯(◯) ◯(◯     ) ◯(◯) ⊚(⊚)     ⊚(⊚) ×(×) ◯(.largec     ircle.) ×(×)  (e) ⊚(⊚)     ◯(◯) ⊚(⊚) .circlein     circle.(⊚) ⊚(⊚) .largecircle     .(◯) ◯(◯) ◯(◯     ) ◯(◯) ⊚(⊚)     ⊚(⊚) ×(×) ◯(.largec     ircle.) ×(×) Test 7  ◯ ◯ .largecircle     . ◯ ◯ ◯ ◯ ◯     ◯ ◯ ◯ Δ ◯ Δ     Light fastness

We claim:
 1. An ink composition comprising a first dye represented byformula (I): ##STR54## wherein R¹ represents a phenyl or naphthyl groupwhich may be substituted by a hydroxyl group, --NH₂, --SO₃ M or --COOMwherein M represents a hydrogen atom or a cation species derived from analkali metal, ammonia or an amine,R² represents a hydrogen, acarboxyalkyl group wherein the carboxy group may form a salt with analkali metal or ammonia, a substituted or unsubstituted alkoxyalkylgroup or a substituted or unsubstitUted phenyl or alkanoyl group, andR³, R⁴ and R⁵, which may be the same or different, each independentlyrepresent a hydrogen atom or --SO₃ M wherein M is as defined above,provided that R¹ does not represent a phenyl group substituted with--SO₃ M when R³, R⁴ and R⁵ all represent --SO₃ M;and a second dyeselected from the group consisting of C.I. Direct Yellow 86, 132 and 144and compounds represented by formula (II): ##STR55## wherein R⁶represents a phenyl or naphthyl group which may be substituted by ahydroxyl group, --NH₂, --SO₃ M or --COOM wherein M represents a hydrogenatom or a cation species derived from an alkali metal, ammonia or anamine, and R⁷ represents a hydrogen atom or --SO₃ M wherein M is asdefined above; or formula III: ##STR56## wherein R⁸ and R⁹, which may bethe same or different, each independently represent a hydrogen atom, analkyl group or a hydroxyalkyl group, provided that R⁸ and R⁹ do notsimultaneously represent a hydrogen atom, and R¹⁰ and R¹¹, which may bethe same or different, each independently represent a hydrogen atom, analkyl group, a hydroxyalkyl group or an alkoxy group; said first dyebeing present in the composition in an amount sufficient to enable thecomposition to form a print image having a black hue on a recordingmedium, said second dye being present in the composition in an amountsufficient to improve vividness of the black hue or sharpness of theimage or both.
 2. An ink composition according to claim 1, wherein inthe dye represented by formula (I), R¹ represents a phenyl or naphthylgroup which may be substituted by a hydroxyl group, --NH₂, --SO₃ M or--COOM wherein M represents a hydrogen atom or a cation species derivedfrom an alkali metal, ammonia or tri (hydroxy C₁₋₆ alkyl) amine,R²represents a carboxyalkyl group wherein the carboxy group may form asalt with an alkali metal or ammonia, a substituted or unsubstitutedC₁₋₆ alkoxy C₁₋₆ alkyl group or a substituted or unsubstituted phenyl orC₁₋₆ alkanoyl group, and R³, R⁴ and R⁵, which may be the same ordifferent, each independently represent a hydrogen atom or --SO₃ Mwherein M is as defined above.
 3. An ink composition according to claim1, wherein said dye represented by formula (I) is contained in an amountof 0.1 to 10% by weight.
 4. An ink composition according to claim 1,wherein said C.I. Direct Yellow 86, 132 or 144 is contained in an amountof 0.001 to 0.5% by weight.
 5. An ink composition according to claim 1,wherein said dye represented by formula (II) is contained in an amountof 0.001 to 0.5% by weight.
 6. An ink composition according to claim 1,wherein said dye represented by formula (III) is contained in an amountof 0.005 to 0.5% by weight.
 7. In a process for ink jet recordingwherein a black ink is ejected onto a recording medium to form a printimage thereon, the improvement comprising ejecting an ink compositiononto the recording medium wherein the composition comprises a first dyerepresented by formula (I): ##STR57## wherein R¹ represents a phenyl ornaphthyl group which may be substituted by a hydroxyl group, --NH₂,--SO₃ M or --COOM wherein M represents a hydrogen atom or a cationspecies derived from an alkali metal, ammonia or an amine,R² representsa hydrogen, a carboxyalkyl group wherein the carboxy group may form asalt with an alkali metal or ammonia, a substituted or unsubstitutedalkoxyalkyl group or a substituted or unsubstituted phenyl or alkanoylgroup, and R³, R⁴ and R⁵, which may be the same or different, eachindependently represent a hydrogen atom or --SO₃ M wherein M is asdefined above, provided that R¹ does not represent a phenyl groupsubstituted with --SO₃ M when R³, R⁴ and R⁵ all represent --SO₃ M;and asecond dye selected from the group consisting of C.I. Direct Yellow 86,132 and 144 and compounds represented by formula (II): ##STR58## whereinR⁶ represents a phenyl or naphthyl group which may be substituted by ahydroxyl group, --NH₂, --SO₃ M or --COOM wherein M represents a hydrogenatom or a cation species derived from an alkali metal, ammonia or anamine, and R⁷ represents a hydrogen atom or --SO₃ M wherein M is asdefined above; or formula III: ##STR59## wherein R⁸ and R⁹, which may bethe same or different, each independently represent a hydrogen atom, analkyl group or a hydroxyalkyl group, provided that R⁸ and R⁹ do notsimultaneously represent a hydrogen atom, and R¹⁰ and R¹¹, which may bethe same or different, each independently represent a hydrogen atom, analkyl group, a hydroxyalkyl group or an alkoxy group; said first dyebeing present in the composition in an amount sufficient to enable thecomposition to form a print image having a black hue on a recordingmedium, said second dye being present in the composition in an amountsufficient to improve vividness of the black hue or sharpness of theimage or both.
 8. An ink composition according to claim 7, wherein inthe dye represented by formula (I), R¹ represents a phenyl or naphthylgroup which may be substituted by a hydroxyl group, --NH₂, --SO₃ M or--COOM wherein M represents a hydrogen atom or a cation species derivedfrom an alkali metal, ammonia or tri(hydroxy C₁₋₆ alkyl) amine,R²represents a carboxyalkyl group wherein the carboxy group may form asalt with an alkali metal or ammonia, a substituted or unsubstitutedC₁₋₆ alkoxy C₁₋₆ alkyl group or a substituted or unsubstituted phenyl orC₁₋₆ alkanoyl group, and R³, R⁴ and R⁵, which may be the same ordifferent, each independently represent a hydrogen atom or --SO₃ Mwherein M is as defined above.
 9. An ink composition according to claim7, wherein said dye represented by formula (I) is present in an amountof 0.1 to 10% by weight.
 10. An ink composition according to claim 7,wherein said C.I. Direct Yellow 86, 132 or 144 is present in an amountof 0.001 to 0.5% by weight.
 11. An ink composition according to claim 7,wherein said dye represented by formula (II) is present in an amount of0.001 to 0.5% by weight.
 12. An ink composition according to claim 7,wherein said dye represented by formula (III) is present in an amount of0.005 to 0.5% by weight.